CN116161880B - Preparation method of carbon-fixation early-strength high-performance magnesium slag-based wet cementing material - Google Patents
Preparation method of carbon-fixation early-strength high-performance magnesium slag-based wet cementing material Download PDFInfo
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- CN116161880B CN116161880B CN202310205828.XA CN202310205828A CN116161880B CN 116161880 B CN116161880 B CN 116161880B CN 202310205828 A CN202310205828 A CN 202310205828A CN 116161880 B CN116161880 B CN 116161880B
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- 239000011777 magnesium Substances 0.000 title claims abstract description 119
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 113
- 239000002893 slag Substances 0.000 title claims abstract description 111
- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 49
- 238000000227 grinding Methods 0.000 claims abstract description 31
- 238000001238 wet grinding Methods 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 18
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000002738 chelating agent Substances 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 239000002699 waste material Substances 0.000 claims abstract description 4
- 238000012360 testing method Methods 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 238000001723 curing Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 18
- 239000011083 cement mortar Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 238000013008 moisture curing Methods 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 12
- 238000012216 screening Methods 0.000 claims description 12
- 238000010998 test method Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000009776 industrial production Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 6
- 230000006641 stabilisation Effects 0.000 abstract description 3
- 238000011105 stabilization Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 25
- 230000001276 controlling effect Effects 0.000 description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 17
- 239000002910 solid waste Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000004568 cement Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000006012 monoammonium phosphate Substances 0.000 description 2
- -1 on the other hand Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910017677 NH4H2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B13/00—Feeding the unshaped material to moulds or apparatus for producing shaped articles; Discharging shaped articles from such moulds or apparatus
- B28B13/02—Feeding the unshaped material to moulds or apparatus for producing shaped articles
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
- C04B5/06—Ingredients, other than water, added to the molten slag or to the granulating medium or before remelting; Treatment with gases or gas generating compounds, e.g. to obtain porous slag
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of low-carbon cementing materials, and discloses a preparation method of a carbon-fixation early-strength high-performance magnesium slag-based wet cementing material, which comprises the following steps: step one: rapidly cooling the discharged waste high-temperature magnesium slag to 450-550 ℃, adding 30-50 parts by mass of Wen Meizha and 2.0-5.0 parts by mass of ammonium dihydrogen phosphate into wet-milling carbon-fixing integrated equipment, and primarily stirring to room temperature; step two: 100 parts by mass of water, 0.2 to 0.5 part by mass of chemical chelating agent and 15 to 100 parts by mass of grinding medium are added into the equipment, the rotating speed is controlled to be 300 to 600r/min, CO 2 gas is synchronously injected at the gas speed of 1.0 to 2.0L/min, and the temperature of the slurry is controlled to be 40 to 80 ℃. According to the preparation method of the carbon-fixing early-strength high-performance magnesium slag-based wet cementing material, high-temperature magnesium slag is rapidly cooled to 450-550 ℃, and finally converted into P 4O6 under the cooperation of ammonium dihydrogen phosphate in a high-temperature environment provided by the high-temperature magnesium slag, and the high-temperature magnesium slag is stirred under the stabilization effect of P 4O6 until the normal temperature is obviously weakened to convert beta-C 2 S in the magnesium slag into a gamma-C 2 S crystal form.
Description
Technical Field
The invention relates to the technical field of low-carbon cementing materials, in particular to a preparation method of a carbon-fixation early-strength high-performance magnesium slag-based wet cementing material.
Background
CO 2 is one of main reasons for generating greenhouse effect, so that various hazards are brought to human living environment, carbon capturing and sealing technology (CCUS) is mature, availability of CO 2 in various fields is realized initially, CO 2 emission in the building field accounts for more than 50% of total emission proportion of CO 2 in the whole country, CO 2 emission and CO 2 mineralization sealing in the building process are reduced to become two currently feasible solutions, and with development of industrial production, resource consumption in the industrial field is further increased, large amounts of industrial solid waste are accumulated to cause soil pollution and waste of land resources, and the trend of preparing cementing materials with different performances by mixing industrial solid waste into the cementing materials is great.
The magnesium slag is used as a common industrial solid waste with annual output of about 360 ten thousand tons, is a powdery substance at normal temperature, is suspended in air, is difficult to settle and is easy to cause dust pollution, the current treatment method of most magnesium factories is to pour the magnesium slag into a barren land or landfill treatment, but the moisture absorption of the magnesium slag is easy to cause soil pollution caused by salinization of soil, and because the content of gamma-C 2 S and MgO in the magnesium slag is higher, the magnesium slag-based cementing material has lower early and medium strength and has extremely high expansibility in the later hydration process, the utilization rate of the magnesium slag in the cementing material is seriously influenced, and researches show that the rapid cooling of the magnesium slag can inhibit the conversion of beta-C 2 S into gamma-C 2 S and the carbon fixation reaction can obviously promote the generation of calcium carbonate, and MgO can react with H + to generate Mg 2+ to form Mg (OH) 2 precipitation.
According to the method, the magnesium slag cementing material and the forming process method thereof are disclosed by the retrieved Chinese patent CN202010738278.4, the NaHCO 3 is added to react calcium salt in the magnesium slag to form calcium carbonate, the problem of strength can not be fundamentally solved, so that strength improvement is not obvious, the method for producing cement clinker by utilizing magnesium slag is also disclosed by the retrieved Chinese patent CN200510074527.X, as most of raw materials are not industrial solid waste, energy consumption is large in the cement firing process and industrial application is not facilitated, and meanwhile, the Chinese patent CN202110573716.0 discloses a preparation method for homogenizing carbonization of the magnesium slag cementing material by a silicon thermal method, hydration expansion of the magnesium slag is inhibited by high-humidity maintenance at normal temperature, but the reaction of MgO and water can only be partially promoted under high-humidity environment, and the problem of hydration expansion of the magnesium slag can not be fundamentally solved.
Disclosure of Invention
(One) solving the technical problems
Aiming at the defects of the prior art, the invention provides the preparation method of the carbon-fixing early-strength high-performance magnesium slag-based wet cementing material, solves the problems of lower strength and volume expansion of the magnesium slag-based cementing material in the middle period before the magnesium slag-based cementing material, realizes the long-term ore storage of CO 2 and the large-scale utilization of magnesium slag, greatly relieves the problems of carbon emission, solid waste storage and the like in China, and has good environmental protection benefit.
(II) technical scheme
In order to achieve the technical problems, the invention provides the following technical scheme: a preparation method of a carbon-fixing early-strength high-performance magnesium slag-based wet cementing material comprises the following steps:
Step one: rapidly cooling the discharged waste high-temperature magnesium slag to 450-550 ℃, adding 30-50 parts by mass of Wen Meizha and 2.0-5.0 parts by mass of ammonium dihydrogen phosphate into wet-milling carbon-fixing integrated equipment, and primarily stirring to room temperature;
Step two: adding 100 parts by mass of water, 0.2-0.5 part by mass of chemical chelating agent and 15-100 parts by mass of grinding medium into the equipment, controlling the rotating speed to be 300-600 r/min, synchronously injecting CO 2 gas at the gas speed of 1.0-2.0L/min, controlling the temperature of the slurry to be 40-80 ℃ until the pH value of the slurry is stabilized to be 6.6-7.4, stopping wet grinding, and screening to obtain the magnesium slag-based cementing material;
Step three: after fully stirring, pouring the magnesium slag-based grinding slurry into a standard clean slurry anti-pressing iron mold with the thickness of 20mm multiplied by 20mm and a plastic mold with the thickness of 20mm multiplied by 60mm, carrying out moisture curing for 2 days, then placing the mold into a curing chamber RH=98+/-2%, curing at the temperature=20+/-2 ℃ until the temperature reaches 3d, 14d and 28d, and testing the obtained test block according to GB/T17671-2021 cement mortar strength test method.
Further, the cooling rate in the first step is more than or equal to 50 ℃/min.
Further, the rotational speed of the preliminary stirring in the first step is 50-100 r/min.
Further, the high-temperature magnesium slag in the first step is a byproduct magnesium slag generated in the production process of the metal magnesium pith river method, and the main components are CaO more than or equal to 53%, mgO more than or equal to 7%, siO 2 more than or equal to 28%, and the median particle size (D 50) =15-30 μm.
Further, in the second step, the chemical chelating agent is one or a combination of a plurality of crystal form regulating agents, namely, polycarboxylic acid high-efficiency water reducing agent, glycine and sodium hexametaphosphate.
Further, in the second step, the grinding medium parameters are as follows: a steel ball with the diameter of 1.0-1.5 mm and a zirconia ball with the diameter of 0.5-1.0 mm are selected to be mixed according to the ratio of 2:1-2:5, and the ball-material ratio is 1:2-2:1.
Further, in the second step, the CO 2 gas is industrial production tail gas, and the purity is more than or equal to 40%.
Further, the median particle diameter (D 50) =5 to 10 μm of the magnesium slag-based cement in the second step.
(III) beneficial effects
Compared with the prior art, the invention provides a preparation method of a carbon-fixing early-strength high-performance magnesium slag-based wet cementing material, which has the following beneficial effects:
1. According to the preparation method of the carbon-fixing early-strength high-performance magnesium slag-based wet cementing material, high-temperature magnesium slag is rapidly cooled to 450-550 ℃, and finally converted into P 4O6 under the cooperation of ammonium dihydrogen phosphate in a high-temperature environment provided by the high-temperature magnesium slag, and the high-temperature magnesium slag is stirred under the stabilization effect of P 4O6 until the normal temperature is obviously weakened to convert beta-C 2 S in the magnesium slag into a gamma-C 2 S crystal form.
2. According to the preparation method of the carbon-fixing early-strength high-performance magnesium slag-based wet cementing material, magnesium slag particles are thinned through a liquid-phase grinding and carbon-fixing technology, the specific surface area of magnesium slag is increased, on one hand, mgO and gamma-C 2 S react with H 3PO4 to generate Mg (OH) 2 sediment and calcium carbonate, on the other hand, NH 3 is extremely easy to dissolve in water to form NH 3·H2O,NH3·H2 O in a liquid-phase state to quickly capture CO 2, so that the content of CO 3 2- in a liquid-phase environment is obviously improved, the reaction rate of beta-C 2 S, a small amount of gamma-C 2 S and CO 2 is accelerated, and the problems of harm of gamma-C 2 S and MgO to the volume stability of the magnesium slag-based cementing material and low early-medium-term strength are fundamentally solved.
3. According to the preparation method of the carbon-fixing early-strength high-performance magnesium slag-based wet cementing material, the slurry reaction temperature can be stabilized at 40-80 ℃ by controlling the gas speed to be 1.0-2.0L/min and the rotating speed to be 300-600 r/min, the adjustability of vaterite crystal form calcium carbonate is realized, the strength of the magnesium slag-based cementing material is further improved, the operation is simple and convenient, the magnesium slag-based cementing materials with different vaterite content types are prepared according to different requirements, and the industrialized application and the universality of magnesium slag are realized.
4. According to the preparation method of the carbon-fixation early-strength high-performance magnesium slag-based wet cementing material, the high additional value utilization of carbon dioxide and solid waste is realized by utilizing the combination of magnesium slag solid waste and CO 2 mineralization sealing treatment.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Test parameter table
In the first embodiment, the specific steps of this embodiment are as follows:
Step one: rapidly cooling the produced high-temperature magnesium slag to 450 ℃, and then adding 30 parts by mass of ammonium dihydrogen phosphate with the height of Wen Meizha and 2.0 parts by mass into wet-milling carbon-fixing integrated equipment to be primarily stirred to room temperature;
Step two: adding 100 parts by mass of water, 0.2 part by mass of chemical chelating agent and 15 parts by mass of grinding medium into the equipment, controlling the rotating speed to be 300r/min, synchronously injecting CO 2 gas at the gas speed of 2.0L/min, controlling the temperature of the slurry to be 40 ℃ until the pH value of the slurry is stabilized at 6.6, stopping wet grinding, and screening to obtain the magnesium slag-based cementing material;
Step three: after fully stirring, pouring the magnesium slag-based grinding slurry into a standard clean slurry anti-pressing iron mold with the thickness of 20mm multiplied by 20mm and a plastic mold with the thickness of 20mm multiplied by 60mm, carrying out moisture curing for 2 days, then placing the mold into a curing chamber RH=98+/-2%, curing at the temperature=20+/-2 ℃ until the temperature reaches 3d, 14d and 28d, and testing the obtained test block according to GB/T17671-2021 cement mortar strength test method.
In the second embodiment, the specific steps of this embodiment are as follows:
step one: rapidly cooling the produced high-temperature magnesium slag to 500 ℃, and then adding 30 parts by mass of ammonium dihydrogen phosphate with the height of Wen Meizha parts by mass and 5.0 parts by mass into wet-milling carbon-fixing integrated equipment to be primarily stirred to room temperature;
step two: adding 100 parts by mass of water, 0.3 part by mass of chemical chelating agent and 60 parts by mass of grinding medium into the equipment, controlling the rotating speed to be 400r/min, synchronously injecting CO 2 gas at the gas speed of 2.0L/min, controlling the temperature of the slurry to be 50 ℃ until the pH value of the slurry is stabilized at 6.8, stopping wet grinding, and screening to obtain the magnesium slag-based cementing material;
Step three: after fully stirring, pouring the magnesium slag-based grinding slurry into a standard clean slurry anti-pressing iron mold with the thickness of 20mm multiplied by 20mm and a plastic mold with the thickness of 20mm multiplied by 60mm, carrying out moisture curing for 2 days, then placing the mold into a curing chamber RH=98+/-2%, curing at the temperature=20+/-2 ℃ until the temperature reaches 3d, 14d and 28d, and testing the obtained test block according to GB/T17671-2021 cement mortar strength test method.
In embodiment three, the specific steps of this embodiment are as follows:
step one: quickly cooling the produced high-temperature magnesium slag to 550 ℃, and then adding 40 parts by mass of ammonium dihydrogen phosphate with the height of Wen Meizha and 4.0 parts by mass into wet-milling carbon-fixing integrated equipment to be primarily stirred to room temperature;
Step two: adding 100 parts by mass of water, 0.5 part by mass of chemical chelating agent and 80 parts by mass of grinding medium into the equipment, controlling the rotating speed to be 600r/min, synchronously injecting CO 2 gas at the gas speed of 1.0L/min, controlling the temperature of the slurry to be 70 ℃, stopping wet grinding until the pH value of the slurry is stabilized at 7.0, and screening to obtain a magnesium slag-based cementing material;
Step three: after fully stirring, pouring the magnesium slag-based grinding slurry into a standard clean slurry anti-pressing iron mold with the thickness of 20mm multiplied by 20mm and a plastic mold with the thickness of 20mm multiplied by 60mm, carrying out moisture curing for 2 days, then placing the mold into a curing chamber RH=98+/-2%, curing at the temperature=20+/-2 ℃ until the temperature reaches 3d, 14d and 28d, and testing the obtained test block according to GB/T17671-2021 cement mortar strength test method.
In the fourth embodiment, the specific steps of this embodiment are as follows:
step one: rapidly cooling the produced high-temperature magnesium slag to 500 ℃, and then adding 40 parts by mass of ammonium dihydrogen phosphate with the height of Wen Meizha and 3.0 parts by mass into wet-milling carbon-fixing integrated equipment to be primarily stirred to room temperature;
step two: adding 100 parts by mass of water, 0.2 part by mass of chemical chelating agent and 15 parts by mass of grinding medium into the equipment, controlling the rotating speed to be 300r/min, synchronously injecting CO 2 gas at the gas speed of 2.0L/min, controlling the temperature of the slurry to be 40 ℃ until the pH value of the slurry is stabilized at 7.2, stopping wet grinding, and screening to obtain the magnesium slag-based cementing material;
Step three: after fully stirring, pouring the magnesium slag-based grinding slurry into a standard clean slurry anti-pressing iron mold with the thickness of 20mm multiplied by 20mm and a plastic mold with the thickness of 20mm multiplied by 60mm, carrying out moisture curing for 2 days, then placing the mold into a curing chamber RH=98+/-2%, curing at the temperature=20+/-2 ℃ until the temperature reaches 3d, 14d and 28d, and testing the obtained test block according to GB/T17671-2021 cement mortar strength test method.
In a fifth embodiment, the specific steps of this embodiment are as follows:
Step one: rapidly cooling the produced high-temperature magnesium slag to 550 ℃, and then adding 30 parts by mass of ammonium dihydrogen phosphate with the height of Wen Meizha parts by mass and 5.0 parts by mass into wet-milling carbon-fixing integrated equipment to be primarily stirred to room temperature;
Step two: adding 100 parts by mass of water, 0.4 part by mass of chemical chelating agent and 60 parts by mass of grinding medium into the equipment, controlling the rotating speed to be 500r/min for wet grinding treatment, synchronously injecting CO 2 gas at the gas speed of 1.5L/min, controlling the temperature of the slurry to be 60 ℃, stopping wet grinding until the pH value of the slurry is stabilized at 7.4, and screening to obtain the magnesium slag-based cementing material;
Step three: after fully stirring, pouring the magnesium slag-based grinding slurry into a standard clean slurry anti-pressing iron mold with the thickness of 20mm multiplied by 20mm and a plastic mold with the thickness of 20mm multiplied by 60mm, carrying out moisture curing for 2 days, then placing the mold into a curing chamber RH=98+/-2%, curing at the temperature=20+/-2 ℃ until the temperature reaches 3d, 14d and 28d, and testing the obtained test block according to GB/T17671-2021 cement mortar strength test method.
In a sixth embodiment, the specific steps of this embodiment are as follows:
Step one: rapidly cooling the produced high-temperature magnesium slag to 450 ℃, and then adding 50 parts by mass of ammonium dihydrogen phosphate with the height of Wen Meizha and 4.0 parts by mass into wet-milling carbon-fixing integrated equipment to be primarily stirred to room temperature;
step two: adding 100 parts by mass of water, 0.3 part by mass of chemical chelating agent and 100 parts by mass of grinding medium into the equipment, controlling the rotating speed to be 400r/min, synchronously injecting CO 2 gas at the gas speed of 2.0L/min, controlling the temperature of the slurry to be 50 ℃ until the pH value of the slurry is stabilized at 6.9, stopping wet grinding, and screening to obtain the magnesium slag-based cementing material;
Step three: after fully stirring, pouring the magnesium slag-based grinding slurry into a standard clean slurry anti-pressing iron mold with the thickness of 20mm multiplied by 20mm and a plastic mold with the thickness of 20mm multiplied by 60mm, carrying out moisture curing for 2 days, then placing the mold into a curing chamber RH=98+/-2%, curing at the temperature=20+/-2 ℃ until the temperature reaches 3d, 14d and 28d, and testing the obtained test block according to GB/T17671-2021 cement mortar strength test method.
In embodiment seven, the specific steps of this embodiment are as follows:
step one: rapidly cooling the produced high-temperature magnesium slag to 500 ℃, and then adding 40 parts by mass of ammonium dihydrogen phosphate with the height of Wen Meizha and 5.0 parts by mass into wet-milling carbon-fixing integrated equipment to be primarily stirred to room temperature;
step two: adding 100 parts by mass of water, 0.5 part by mass of chemical chelating agent and 100 parts by mass of grinding medium into the equipment, controlling the rotating speed to be 600r/min, synchronously injecting CO 2 gas at the gas speed of 1.0L/min, controlling the temperature of the slurry to be 70 ℃ until the pH value of the slurry is stabilized at 7.1, stopping wet grinding, and screening to obtain a magnesium slag-based cementing material;
Step three: after fully stirring, pouring the magnesium slag-based grinding slurry into a standard clean slurry anti-pressing iron mold with the thickness of 20mm multiplied by 20mm and a plastic mold with the thickness of 20mm multiplied by 60mm, carrying out moisture curing for 2 days, then placing the mold into a curing chamber RH=98+/-2%, curing at the temperature=20+/-2 ℃ until the temperature reaches 3d, 14d and 28d, and testing the obtained test block according to GB/T17671-2021 cement mortar strength test method.
In a first comparative example, which was not doped with monoammonium phosphate, the comparative example comprises the following steps:
step one: quickly cooling the produced 30 parts by mass of Wen Meizha parts by mass to room temperature;
Step two: adding 100 parts by mass of water, 0.2 part by mass of chemical chelating agent and 15 parts by mass of grinding medium into wet grinding and carbon fixing integrated equipment, controlling the rotating speed to be 300r/min, synchronously injecting Co 2 gas at the gas speed of 2.0L/min, controlling the temperature of the slurry to be 40 ℃, stopping wet grinding until the pH value of the slurry is stabilized at 7.0, and screening to obtain a magnesium slag-based cementing material;
Step three: after fully stirring, pouring the magnesium slag-based grinding slurry into a standard clean slurry anti-pressing iron mold with the thickness of 20mm multiplied by 20mm and a plastic mold with the thickness of 20mm multiplied by 60mm, carrying out moisture curing for 2 days, then placing the mold into a curing chamber RH=98+/-2%, curing at the temperature=20+/-2 ℃ until the temperature reaches 3d, 14d and 28d, and testing the obtained test block according to GB/T17671-2021 cement mortar strength test method.
A second comparative example, which includes the following steps, was not wet-milled:
Step one: rapidly cooling the produced high-temperature magnesium slag to 500 ℃, and then adding 30 parts by mass of high Wen Meizha parts by mass of ammonium dihydrogen phosphate into stirring equipment to be primarily stirred to room temperature;
Step two: adding 0.3 part by mass of chemical chelating agent and 60 parts by mass of grinding medium into the stirring equipment, synchronously injecting CO 2 gas at a gas speed of 2.0L/min until the pH value of the slurry is stable to 7.0, stopping wet grinding, and screening to obtain a magnesium slag-based cementing material;
Step three: after fully stirring, pouring the magnesium slag-based grinding slurry into a standard clean slurry anti-pressing iron mold with the thickness of 20mm multiplied by 20mm and a plastic mold with the thickness of 20mm multiplied by 60mm, carrying out moisture curing for 2 days, then placing the mold into a curing chamber RH=98+/-2%, curing at the temperature=20+/-2 ℃ until the temperature reaches 3d, 14d and 28d, and testing the obtained test block according to GB/T17671-2021 cement mortar strength test method.
Comparative example three, without carbon treatment, includes the following steps:
step one: quickly cooling the produced high-temperature magnesium slag to 550 ℃, and then adding 40 parts by mass of ammonium dihydrogen phosphate with the height of Wen Meizha and 4.0 parts by mass into wet-milling carbon-fixing integrated equipment to be primarily stirred to room temperature;
Step two: adding 100 parts by mass of water, 0.5 part by mass of chemical chelating agent and 80 parts by mass of grinding medium into wet grinding and carbon fixing integrated equipment, controlling the rotating speed to be 600r/min, stopping wet grinding until the pH value of the slurry is stabilized at 7.0, and screening to obtain a magnesium slag-based cementing material;
Step three: after fully stirring, pouring the magnesium slag-based grinding slurry into a standard clean slurry anti-pressing iron mold with the thickness of 20mm multiplied by 20mm and a plastic mold with the thickness of 20mm multiplied by 60mm, carrying out moisture curing for 2 days, then placing the mold into a curing chamber (RH=98+/-2%, temperature=20+/-2 ℃) for curing until 3d, 14d and 28d, and testing the obtained test block according to GB/T17671-2021 cement mortar strength test method.
Summary of test data
From the above table, the comparative example 1, in which the incorporation of the raw material monoammonium phosphate was removed on the basis of example 1, is inferior in stability of the concrete, the comparative example 2, in which the liquid-phase grinding treatment was not performed on the basis of example 2, is inferior in mechanical properties of the concrete, and the comparative example 3, in which the carbon dioxide treatment was not performed, is significantly reduced in test performance.
The 28d expansion rates of the embodiments 1 to 7 are all lower than 0.03%, the 3d compressive strength is 24.5 to 33.1MPa, and the 28d compressive strength is 30.5 to 39.4MPa, so that the preparation method of the high-stability early-strength magnesium slag-based wet-process solid-carbon gelling material provided by the invention can solve the problem of volume expansion of the magnesium slag after being mixed with cement and improve the strength of concrete on the basis of realizing comprehensive utilization of the magnesium slag and carbon sealing, and further, in the embodiment 7, the performance of the gelling material is optimal by optimizing experimental conditions.
The basic principle of the invention is as follows:
The high-temperature slag produced just is cooled to 450-550 ℃ through water bath, on one hand, decomposition of ammonium dihydrogen phosphate is promoted to form NH 3 and H 3PO4 (1) under high temperature, H 3PO4 is reacted to convert HPO 3 and aggregate in a large amount under high temperature, and P 4O6 is generated by HPO 3)n under the condition of low oxygen content under high temperature.
NH4H2PO4———H3PO4+NH3 (1)
2H3PO4———H4P2O7+H2O3 (2)
H4P2O7———2HPO3+H2O (3)
2(HPO3)n———n/2P4O6+nH2O+nO2 (4)
On the other hand, the beta-C 2 S can obviously weaken the conversion to the crystal form of gamma-C 2 S under the double effects of rapid cooling and P 4O6, and then the liquid phase grinding and carbon fixation technology is adopted, on the one hand, the cooled magnesium slag is fully refined, the specific surface area is increased, mgO in the magnesium slag reacts with H 3PO4 to promote the dissolution of Mg 2+ ions, the reaction with OH - ions to form Mg (OH) 2 precipitation, on the other hand, NH 3 is extremely easy to dissolve in water to form NH 3·H2O,NH3·H2 O, the dissolution rate of CO 2 in water can be promoted, the concentration of CO 3 2- in the solution is improved, the proportion of local CO 3 2-/Ca2+ is increased, meanwhile, the formation of metastable crystal form vaterite is induced through the regulation of the gas rate and the rotation speed of a stirring rod, and the carbonization activity of composite solid waste is enhanced.
The beneficial effects of the invention are as follows:
According to the preparation method of the carbon-fixing early-strength high-performance magnesium slag-based wet cementing material, high-temperature magnesium slag is rapidly cooled to 450-550 ℃, and finally converted into P 4O6 under the cooperation of ammonium dihydrogen phosphate in a high-temperature environment provided by the high-temperature magnesium slag, and the high-temperature magnesium slag is stirred under the stabilization effect of P 4O6 until the normal temperature is obviously weakened to convert beta-C 2 S in the magnesium slag into a gamma-C 2 S crystal form.
And by liquid-phase grinding and carbon fixation technology, magnesium slag particles are thinned, the specific surface area of magnesium slag is increased, on one hand, mgO and gamma-C 2 S are promoted to react with H 3PO4 to generate Mg (OH) 2 precipitate and calcium carbonate, on the other hand, NH 3 is very easy to dissolve in water to form NH 3·H2O,NH3·H2 O in a liquid-phase state, so that CO 2 can be quickly captured, the content of CO 3 2- in a liquid-phase environment is obviously improved, the reaction rate of beta-C 2 S and a small amount of gamma-C 2 S with CO 2 is accelerated, and the problems of harm of gamma-C 2 S and MgO to the volume stability of magnesium slag-based cementing materials and low early-medium-stage strength are fundamentally solved.
Meanwhile, the reaction temperature of the slurry can be stabilized at 40-80 ℃ by controlling the gas speed to be 1.0-2.0L/min and the rotating speed to be 300-600 r/min, the adjustability of the vaterite crystal form calcium carbonate is realized, the strength of the magnesium slag-based cementing material is further improved, the operation is simple and convenient, the magnesium slag-based cementing materials with different vaterite content types are prepared according to different requirements, and the industrialized application and the universality of the magnesium slag are realized.
And the high added value utilization of carbon dioxide and solid waste is realized by utilizing the magnesium slag solid waste and combining CO 2 mineralization and sealing treatment.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The preparation method of the carbon-fixing early-strength high-performance magnesium slag-based wet cementing material is characterized by comprising the following steps of:
Step one: quickly cooling waste magnesium slag discharged at high temperature to 450-550 ℃, adding 30-50 parts by mass of Wen Meizha and 2.0-5.0 parts by mass of ammonium dihydrogen phosphate into wet-milling carbon-fixing integrated equipment, and primarily stirring to room temperature;
Step two: adding 100 parts by mass of water, 0.2-0.5 part by mass of chemical chelating agent and 15-100 parts by mass of grinding medium into the equipment, controlling the rotating speed to be 300-600 r/min, synchronously injecting CO 2 gas at the gas speed of 1.0-2.0L/min, controlling the temperature of the slurry to be 40-80 ℃ until the pH value of the slurry is stabilized to be 6.6-7.4, stopping wet grinding, and screening to obtain the magnesium slag-based cementing material;
Step three: after fully stirring, pouring the magnesium slag-based grinding slurry into a standard clean slurry anti-pressing iron mold with the thickness of 20mm multiplied by 20mm and a plastic mold with the thickness of 20mm multiplied by 60mm, carrying out moisture curing for 2 days, then placing the mold into a curing chamber RH=98+/-2%, curing at the temperature=20+/-2 ℃ until the temperature reaches 3d, 14d and 28d, and testing the obtained test block according to GB/T17671-2021 cement mortar strength test method.
2. The method for preparing the carbon-fixing early-strength high-performance magnesium slag-based wet cementing material, which is characterized by comprising the following steps of: in the first step, the cooling rate is more than or equal to 50 ℃/min.
3. The method for preparing the carbon-fixing early-strength high-performance magnesium slag-based wet cementing material, which is characterized by comprising the following steps of: the rotating speed of the primary stirring in the first step is 50-100 r/min.
4. The method for preparing the carbon-fixing early-strength high-performance magnesium slag-based wet cementing material, which is characterized by comprising the following steps of: the high-temperature magnesium slag in the first step is a byproduct magnesium slag generated in the production process of the metal magnesium Pijiang method, and the main components are CaO more than or equal to 53%, mgO more than or equal to 7%, siO 2 more than or equal to 28%, and the median particle size (D 50) =15-30 μm.
5. The method for preparing the carbon-fixing early-strength high-performance magnesium slag-based wet cementing material, which is characterized by comprising the following steps of: in the second step, the chemical chelating agent is one or a combination of a plurality of crystal form regulator polycarboxylic acid high efficiency water reducing agent, glycine and sodium hexametaphosphate.
6. The method for preparing the carbon-fixing early-strength high-performance magnesium slag-based wet cementing material, which is characterized by comprising the following steps of: the grinding medium parameters in the second step are as follows: a steel ball with the diameter of 1.0-1.5 mm and a zirconia ball with the diameter of 0.5-1.0 mm are selected to be mixed according to the ratio of 2:1-2:5, and the ball-material ratio is 1:2-2:1.
7. The method for preparing the carbon-fixing early-strength high-performance magnesium slag-based wet cementing material, which is characterized by comprising the following steps of: in the second step, the CO 2 gas is industrial production tail gas, and the purity is more than or equal to 40%.
8. The method for preparing the carbon-fixing early-strength high-performance magnesium slag-based wet cementing material, which is characterized by comprising the following steps of: and in the second step, the median particle size (D 50) =5-10 μm of the magnesium slag-based cementing material.
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